EP1871438B1 - Materiaux composites a base de polymere et de ceramique destines a etre utilises dans des dispositifs medicaux - Google Patents

Materiaux composites a base de polymere et de ceramique destines a etre utilises dans des dispositifs medicaux Download PDF

Info

Publication number
EP1871438B1
EP1871438B1 EP20060717874 EP06717874A EP1871438B1 EP 1871438 B1 EP1871438 B1 EP 1871438B1 EP 20060717874 EP20060717874 EP 20060717874 EP 06717874 A EP06717874 A EP 06717874A EP 1871438 B1 EP1871438 B1 EP 1871438B1
Authority
EP
European Patent Office
Prior art keywords
medical device
sol
ceramic
polymer
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP20060717874
Other languages
German (de)
English (en)
Other versions
EP1871438A1 (fr
Inventor
Liliana Atanasoska
Scott Schewe
Robert Warner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Boston Scientific Ltd Barbados
Original Assignee
Boston Scientific Ltd Barbados
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Boston Scientific Ltd Barbados filed Critical Boston Scientific Ltd Barbados
Publication of EP1871438A1 publication Critical patent/EP1871438A1/fr
Application granted granted Critical
Publication of EP1871438B1 publication Critical patent/EP1871438B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing

Definitions

  • the present invention relates to new and improved materials for the construction of medical devices.
  • balloons mounted on the distal ends of catheters are widely used in medical treatment.
  • a balloon of this type may be used, for example, to widen a vessel into which the catheter is inserted or to force open a blocked vessel.
  • the requirements for the strength and size of the balloon vary widely depending on the balloon's intended use and the vessel size into which the catheter is inserted.
  • balloon angioplasty e.g., percutaneous transluminal coronary angioplasty or "PCTA”
  • PCTA percutaneous transluminal coronary angioplasty
  • the medical device community is exploring nanotechnology to enhance medical device performance. For example, in various instances, attempts have been made to incorporate nanoparticles into medical devices through the use of blending and compounding techniques. In some situations, the results have been disappointing, largely due to uneven distribution of the nanoparticles within the material.
  • a sol-gel derived bioactive glass polymer composite has become known.
  • the composite can be formed from a bioactive sol-gel solution including a biocompatible polymer.
  • implantable or insertable medical devices which contain or consist of one or more composite regions. These composite regions, in turn, are formed of a hybrid material that includes a combination of polymer comprising segments of polyamide and sol-gel derived ceramic.
  • An advantage of the present invention is that medical devices can be provided with composite regions, which provide for enhanced mechanical characteristics, including enhanced strength, toughness and/or abrasion resistance.
  • the present invention provides implantable or insertable medical devices containing or consisting of one or more composite regions, which contain or consist of a hybrid material that comprises polymer and ceramic as defined in the claims.
  • the composite regions may provide, for example, a variety of enhanced mechanical characteristics, including enhanced strength, toughness and abrasion resistance.
  • Medical devices for use in conjunction with the present invention include a wide variety of implantable or insertable medical devices, which are implanted or inserted either for procedural uses or as implants.
  • examples include balloons, catheters (e.g., renal or vascular catheters such as balloon catheters), guide wires, filters (e.g., vena cava filters), stents (including coronary artery stents, peripheral vascular stents such as cerebral stents, urethral stents, ureteral stents, biliary stents, tracheal stents, gastrointestinal stents and esophageal stents), stent grafts, vascular grafts, vascular access ports, embolization devices including cerebral aneurysm filler coils (including Guglilmi detachable coils and metal coils), myocardial plugs, pacemaker leads, left ventricular assist hearts and pumps, total artificial hearts, heart valves, vascular valve
  • the medical devices of the present invention include implantable and insertable medical devices that are used for diagnosis, for systemic treatment, or for the localized treatment of any tissue or organ.
  • Non-limiting examples are tumors; organs including the heart, coronary and peripheral vascular system (referred to overall as “the vasculature"), the urogenital system, including kidneys, bladder, urethra, ureters, prostate, vagina, uterus and ovaries, eyes, lungs, trachea, esophagus, intestines, stomach, brain, liver and pancreas, skeletal muscle, smooth muscle, breast, dermal tissue, cartilage, tooth and bone.
  • treatment refers to the prevention of a disease or condition, the reduction or elimination of symptoms associated with a disease or condition, or the substantial or complete elimination of a disease or condition.
  • Typical subjects also referred to as “patients” are vertebrate subjects, more typically mammalian subjects and even more typically human subjects.
  • the composite regions correspond to entire medical devices. In other embodiments, the composite regions correspond to one or more medical device portions.
  • the composite regions can be in the form of one or more strands which are incorporated into a medical device, in the form of one or more layers formed over all or only a portion of an underlying medical device substrate, and so forth. Layers can be provided over an underlying substrate in a variety of locations, and in a variety of shapes (e.g., in desired patterns), and they can be formed from a variety of composite materials (e.g., different composite compositions may be provided at different locations).
  • Materials for use as underlying medical device substrates include polymeric materials, ceramic materials and metallic materials, as well as other inorganic materials such as carbon- or silicon-based materials.
  • a "layer" of a given material is a region of that material whose thickness is small compared to both its length and width.
  • a layer need not be planar, for example, taking on the contours of an underlying substrate. Layers can be discontinuous (e.g., patterned).
  • FIG 1 is an exterior view of a balloon catheter 100.
  • Catheter 100 is shown for the purpose of aiding in the understanding of the present invention and a wide variety of other medical devices, including other catheters, are within the scope of the invention.
  • the catheter 100 shown includes a Luer assembly 110 having a Luer port 114 for liquid introduction and a hub 116 for guide-wire 112 introduction and for manipulation of the catheter 100.
  • the Luer assembly 110 allows for access to the catheter lumen, such as the injection of inflation fluids or drugs, or the introduction of a guide wire 112.
  • the balloon catheter 100 illustrated comprises a distal portion 102 that includes a balloon 120.
  • the distal portion 102 may be of any desired length.
  • the catheter 100 is provided with a composite region in accordance with the invention, which is in the form of a coating 102c that extends over the entire surface of the distal portion 102.
  • a therapeutic agent is disposed within or beneath the composite regions, in which cases the composite regions may be referred to as carrier regions or barrier regions.
  • composite carrier region is meant a composite region which further comprises a therapeutic agent and from which the therapeutic agent is released.
  • composite barrier region is meant a composite region which is disposed between a source of therapeutic agent and a site of intended release, and which controls the rate at which therapeutic agent is released.
  • the medical device consists of a composite barrier region that surrounds a source of therapeutic agent.
  • the composite barrier region is disposed over a source of therapeutic agent, which is in turn disposed over all or a portion of a medical device substrate.
  • the composite regions of the present invention are formed of hybrid materials that contain a combination of polymer and ceramic.
  • the composite regions can contain bi-continuous polymeric and ceramic phases, domains of a ceramic phase may be dispersed in a polymer matrix, domains of a polymer phase may be dispersed in domains of a ceramic matrix.
  • the best material properties are obtained when the polymer and ceramic are present in bi-continuous phases, that is, where the ceramic and polymer networks interpenetrate, apparently to the molecular level, so that separate domains are not observed under field emission microscopy or even under transmission electron microscopy.
  • a separate dispersed phase when a separate dispersed phase is present, it desirably will be of nanoscale dimension by which is meant that at least one cross-sectional dimension of the dispersed phase (e.g., the diameter for a spherical or cylindrical phase, the thickness for a ribbon- or plate-shaped phase, etc.) is less than 1 micron (1000 nm), for instance in the range of 0.1 nm to 500 nm, or 1-10 nm. A decrease in such dimensions generally results in an increase in the interfacial area that exists between the polymeric and ceramic phases.
  • multiple polymer and/or ceramic phases may be present.
  • multiple polymer phases may exist where the composite region contains a block copolymer or a blend of different polymers.
  • Polymers for use in the composite regions of the present invention can have a variety of architectures, including cyclic, linear and branched architectures.
  • Branched architectures include star-shaped architectures (e.g., architectures in which three or more chains emanate from a single branch point), comb architectures (e.g., architectures having a main chain and a plurality of side chains) and dendritic architectures (e.g., arborescent and hyperbranched polymers), among others.
  • the polymers for use in the composite regions of the present invention can contain, for example, homopolymer chains, which contain multiple copies of a single constitutional unit, and/or copolymer chains, which contain multiple copies of at least two dissimilar constitutional units, which units may be present in any of a variety of distributions including random, statistical, gradient and periodic (e.g., alternating) distributions.
  • Polymers containing two or more differing homopolymer or copolymer chains are referred to herein as "block copolymers.”
  • Polymers for use in the composite regions of the present invention comprise segments of polyamide and may be selected, for example, from one or more of the following: polycarboxylic acid polymers and copolymers including polyacrylic acids; acetal polymers and copolymers; acrylate and methacrylate polymers and copolymers (e.g., n-butyl methacrylate); cellulosic polymers and copolymers, including cellulose acetates, cellulose nitrates, cellulose propionates, cellulose acetate butyrates, cellophanes, rayons, rayon triacetates, and cellulose ethers such as carboxymethyl celluloses and hydroxyalkyl celluloses; polyoxymethylene polymers and copolymers; polyimide polymers and copolymers such as polyether block imides and polyether block amides, polyamidimides, polyesterimides, and polyetherimides; polysulfone polymers and copolymers including polyarylsulfones and
  • Patent No. 6,545,097 to Pinchuk polyvinyl ketones, polyvinylcarbazoles, and polyvinyl esters such as polyvinyl acetates; polybenzimidazoles; ethylene-methacrylic acid copolymers and ethylene-acrylic acid copolymers, where some of the acid groups can be neutralized with either zinc or sodium ions (commonly known as ionomers); polyalkyl oxide polymers and copolymers including polyethylene oxides (PEO); polyesters including polyethylene terephthalates and aliphatic polyesters such as polymers and copolymers of lactide (which includes lactic acid as well as d-,1- and meso lactide), epsilon-caprolactone, glycolide (including glycolic acid), hydroxybutyrate, hydroxyvalerate, para-dioxanone, trimethylene carbonate (and its alkyl derivatives), 1,4-dioxepan-2-one, 1,5-dio
  • Ceramic materials typically are networks of metal or semi-metal oxides or mixed oxide compounds.
  • suitable metals and semi-metals include silicon, zirconium, titanium, aluminum, tin, hafnium, tantalum, molybdenum, tungsten, rhenium and/or iridium oxides, among others.
  • metal/semi-metal atoms designated generally herein as M
  • M-O-M linkages although other interactions are also commonly present including, for example, hydrogen bonding due to the presence of hydroxyl groups such as residual M-OH groups within the ceramic phases.
  • the ceramic employed within the composite regions of the present invention is formed using sol-gel techniques.
  • the precursor materials used are typically inorganic metallic and semi-metallic salts, metallic and semi-metallic complexes/chelates (e.g., metal acetylacetonate complexes), metallic and semi-metallic hydroxides, or organometallic and organo-semi-metallic compounds (e.g., metal alkoxides and silicon alkoxides and acyloxides). Silicon alkoxides and acyloxides are beneficial due to the variety of formulation options, including co-condensation with related compounds having strong stable C-Si bonds and which can form a strong link between the polymeric and ceramic networks.
  • precursor materials such as those described above are subjected to hydrolysis and condensation (also referred to as polymerization) reactions to form a colloidal suspension, or "sol.”
  • a colloidal suspension or "sol.”
  • an alkoxide of choice such as a methoxide, ethoxide, isopropoxide, tert-butoxide, etc.
  • a semi-metal or metal of choice such as silicon, aluminum, zirconium, titanium, tin, hafnium, tantalum, molybdenum, tungsten, rhenium, iridium, etc.
  • a suitable solvent for example, in one or more alcohols.
  • a sol is formed, for example, by adding water or another aqueous solution, such as an acidic or basic aqueous solution (which aqueous solution can further contain organic solvent species such as alcohols), causing hydrolysis and condensation to occur, thereby forming a sol.
  • additional agents can be added, such as agents to control the viscosity and/or surface tension of the sol.
  • the reaction is basically a ceramic network forming process (from G. Kickelbick, "Concepts for the incorporation of inorganic building blocks into organic polymers on a nanoscale" Prog. Polym. ScL, 28 (2003) 83-114 ):
  • R may be a hydrocarbon group, suitably an alkyl group of form 1-20 carbon atoms which optionally may be interrupted with one or more ether oxygen atoms, or an acyl group, for instance formyl, acetyl or benzoyl.
  • n is suitably equal to a valence of M and m is a positive number between 0 and n.
  • the sol may also be a solvent soluble siloxane oligomer composition, for instance prepared by methods described in US 2,490,691, Langwaiter ; US 4,950,779, Wengrovius ; US 6,140,445, Su et al ; and US 6,323,277, Petty et al , or may be obtained by further condensation/hydrolysis reactions of such oligomers.
  • sol enables solid materials to be made in a variety of different forms.
  • thin films can be produced on a substrate by spray coating, coating with an applicator (e.g., by roller or brush), spin-coating, dip-coating, and so forth, of the sol onto the substrate, whereby a "wet gel" is formed.
  • an applicator e.g., by roller or brush
  • spin-coating e.g., by roller or brush
  • dip-coating e.g., by roller or brush
  • the rate of withdrawal from the sol can be varied to influence the properties of the film.
  • Monolithic wet gels can be formed, for example, by placing the sol into or onto a mold or another form (e.g., a sheet) from which the dried gel can be released. The wet gel is then dried.
  • a material commonly called an "aerogel” is obtained. If the gel is dried via freeze drying (lyophilization), the resulting material is commonly referred to as a "cryogel.” Drying at ambient temperature and ambient pressure leads to what is commonly referred to as a "xerogel.” Other drying possibilities are available including elevated temperature drying (e.g., in an oven), vacuum drying (e.g., at ambient or elevated temperatures), and so forth.
  • TEOS tetraethoxysilane
  • TMOS tetramethoxysilane
  • the polymer has substantial non-covalent interactions with the ceramic phase (e.g., due to hydrogen bonding between hydroxyl groups and electronegative atoms within the polymeric and ceramic phases), which prevent macroscopic phase separation.
  • nanoscale phase domains are best achieved by providing covalent interactions between the polymeric and ceramic networks.
  • This result can be achieved via a number of known techniques, including the following: (a) providing species with both polymer and ceramic precursor groups and thereafter conducting polymerization and hydrolysis/condensation simultaneously, (b) providing a ceramic sol with polymer precursor groups (e.g., groups that are capable of participation in a polymerization reaction, such as vinyl groups or cyclic ether groups) and thereafter conducting an organic polymerization step, and/or (c) providing polymers with ceramic precursor groups (e.g., groups that are capable of participation in hydrolysis/condensation, such as metal or semi-metal alkoxide groups), followed by hydrolysis/condensation of the precursor groups.
  • polymer precursor groups e.g., groups that are capable of participation in a polymerization reaction, such as vinyl groups or cyclic ether groups
  • ceramic precursor groups e.g., groups that are capable of participation in hydrolysis/condensation, such as metal or semi
  • an organic/ceramic hybrid composite is prepared by dissolving an organic polymer component in a suitable solvent and adding a ceramic sol precursor.
  • the ratio of the organic polymer component to the ceramic sol precursor may be range from 95/5 to 5/95 on a weight basis, for instance from 80/20 to 20/80.
  • a solution of a strong acid in water is provided to accomplish hydrolysis and condensation of the ceramic sol precursor.
  • the water is provided at a ratio of approximately one mole water per alkoxy equivalent in the ceramic sol source.
  • the mixture may be stirred under reflux to form the sol, for instance for 4 -24 hrs, after which it is used to prepare a coating, for instance by casting or coating onto a medical device substrate.
  • the coating is thoroughly dried, optionally with addition of heat and/or vacuum to remove the solvent, and aged for several weeks to allow substantial completion of the ceramic condensation reaction.
  • the organic polymer may be, for instance, a Pebax® block copolymer such as the Pebax® grades 2533, 3533 or 4033, or a mixture thereof.
  • the solvent may be an alcohol solvent such as butanol, propanol, or cyclohexanol or an amide solvent such as dimethylacetamide or a mixture of two or more such solvents.
  • the ceramic sol precursor may be for instance tetraethoxysilane, zirconium isopropoxide, titanium isopropoxide or a mixture thereof.
  • the strong acid may be for instance HCL at 0.05-0.3 moles per liter.
  • the resulting coating has a good combination of toughness, adhesion to the substrate material and abrasion resistance.
  • hybrid species which contain groups that can readily participate in each of these reactions.
  • hybrid species also typically contain additional groups, such as -M(OR) x groups.
  • M is a metal or semi-metal as previously defined
  • x is an integer whose value is at least one less than the valence n of M, typically ranging from 1 to 5 (x may be less than n-1 if the same M atom is attached to the hybrid species by more than one bond or is also bonded to one or more monovalent carbon-linked organo groups such as methyl, ethyl, styrylethyl, methacryloxypropyl, glycidoxypropyl, alkylamino, allyl or vinyl), and the various R groups, which may be the same or different, are hydrocarbon or acyl groups, for instance linear, branched or cyclic alkyl groups, aromatic groups or alkyl-aromatic groups of 1 to 10 carbon atoms, and preferably linear or branched alkyl groups having from 1 to 6 carbons, e.g., methyl, ethyl
  • hybrid species include styrylethyltrimethoxysilane: 3-methacryloyloxypropyltrimethoxysilane: glycidoxypropyltrimethoxysiliane: acryloxypropyltrimethoxysilane, and vinyltrimethoxysilane, as well as functionalized oligomers such as described in US 2,490,691, Langwaiter , US 4,950,779, Wengrovius ; US 5,282,998, Horn, et al ; US 5,210,168, Bergstrom et al , US 6,140,445, Su et al ; and US 6,323,277, Petty et al .
  • hybrid species may be combined, for example, with (a) one or more optional organic monomers, for instance, vinyl-group-containing monomers (e.g., styrene, among many others), vinylidene-group-containing monomers (e.g., an alkyl (meth)acrylate, an epoxy functional (meth)acrylate, a urethane dimethacrylate and/or a hydroxyakyl (meth)acrylate), cyclic ether monomers (e.g., where y is 1 to 5, including ethylene oxide, propylene oxide and tetrahydrofuran, and various epoxy functional compounds, especially compounds having two or more epoxy groups per molecule), polyisocyanates, polyamines, polyols and/or diorganosiloxane oligomers (e.g.the cyclic hexamethyl trisiloxane, and octamethyl tetrasiloxane, as well as various linear diorganosiloxane
  • composite materials having polymeric and ceramic phases from a mixture of 3-MPS, methyl methacrylate, TEOS, water, acid, and benzyol peroxide.
  • the hybrid species already has both polymerizable organo and sol-forming -M(OR)x groups on the same molecule, in some cases one or the other of the additional components a) and b) may be avoided, especially if the hybrid species is a functionalized oligomer.
  • Hybrid species can also be used to form composite regions in accordance with routes (b) and (c) described above. For instance, in some cases, such hybrid species are first used to provide a ceramic phase (which contains the organic polymer precursor groups found in the hybrid species) followed by organic polymerization, typically in the presence of one or more comonomers.
  • a hybrid species containing one or more polymerizable organic groups such as a vinyl, vinylidene, cyclic ether or siloxane groups, and one or more inorganic groups, such as - M(OR)x groups (e.g., 3-MPS, SES or 3 -GPS, among others) may be combined with a organometallic compound such as a compound of the formula M(OR)n (e.g., TEOS or TMOS) in the presence of water and an acid catalyst such that hydrolysis and condensation take place.
  • a compound of the formula M(OR)n e.g., TEOS or TMOS
  • ceramic phases maybe formed which have a range of groups that are capable of participation in polymerization reactions with a range of comonomers, including vinyl-, vinylidene-, cyclic ether- and siloxane-containing monomers, via a range of organic polymerization reactions, including thermal, photochemical, anionic, cationic and radical polymerization methods, such as azobis(isobutyronitrile)- or peroxide-initiated polymerizations and controlled/'living" radical polymerizations, for instance, metal-catalyzed atom transfer radical polymerization (ATRP), stable free-radical polymerization (SFRP), nitroxide- mediated processes (NMP), and degenerative transfer (e.g., reversible addition- fragmentation chain transfer (RAFT)) processes, among others.
  • thermal, photochemical, anionic, cationic and radical polymerization methods such as azobis(isobutyronitrile)- or peroxide-initiated polymerizations and controlled/'
  • Step-growth polymerizations such as condensation polymerizations to form polyesters or polyamides, reactions of polyisocyanates and polyols or polyamines to form polyurethane and polyureas, reactions of polyepoxides with polyols, polyamines or polysulf[iota]des, and Michael additions of polyamines to compounds having multiple acrylate, maleate, tumerate or nadic groups thereon are further examples of polymerization reactions that may be employed.
  • polymers may be provided with inorganic groups that are capable of participation in hydrolysis/condensation, thereby becoming intimately associated with the ceramic phase.
  • hybrid species such as those discussed above may be employed in organic polymerization reactions via suitable polymerization techniques such as those listed above, typically in the presence of one or more comonomers.
  • the inorganic groups incorporated into the resulting polymer are then available to participate in hydrolysis/condensation, e.g., using techniques such as those discussed above, thereby forming a ceramic phase that is covalently linked to the polymeric phase.
  • preexisting polymers participate in, or provided with inorganic groups that are capable of participating in the hydrolysis/condensation of the ceramic sol.
  • polyol polymers i.e. polymers having 2 or more carbon-linked hydroxyl groups thereon, can be provided with - M(OR)x groups for participation in sol-gel processing.
  • Such polyol polymers include polyether polyols and polyester polyols. Hydroxy groups of a polyol compound may be directly reacted with a compound such as TEOS or tetraethoxytitanate, forinstance in the manner of V. Munchow, et al, "Poly[(oligoethylene glycol) dihydroxytitanate] as organic-inorganic polymer - electrolytes," Electrochimica Acta, 45 (2000) 1211-1221 .
  • hydroxyl groups of a polyol compound such as polymeric polyol can be reacted with a hybrid species to form terminal or pendant groups which are capable of participation in sol/gel hydrolysis/condensation.
  • Epoxy functionalized hydrolyzable silane compounds such as 3 -GP S can also be reacted with polyols to give analogous -M(OR)n-1 terminated compounds, for instance - M(OR)n-1 terminated polyethers.
  • the resulting polymer is subjected to an additional polymerization step.
  • a polyether with pendant -M(OR)x groups e.g., a 3-GPS modified polyether having pendant -Si(OEt)3 groups
  • a polyamide forming monomer e.g., laurolactam
  • additional polyol polymer optionally with additional polyol polymer
  • Polyol polymers are useful components of the compositions employed in the invention because they are amenable to compounding with ceramics, and can form hydrogen bonds with the ceramic network even in cases where they are not covalently linked thereto. This helps prevent macro-domain phase separation of the polymer and ceramic phases. In many cases they are also capable of participating in further polymerization or crosslinking reactions including reaction with polyisocyanates, polyepoxides and the like.
  • polymer materials that are commonly used in medical devices have hydroxyl, amide, carboxylic acid or other groups capable of forming hydrogen bonds with the ceramic network which can stabilize the system against macro-domain phase separation.
  • polyether-block-polyamides e.g., PEBAX
  • polyesters e.g., polyethylene terephthalate
  • Ether and ester functionalities may also form hydrogen bonds with residual MOH groups in the ceramic phase.
  • a component of the sol-gel ceramic may be a catalyst for a concurrent organic polymerization reaction, or a polymer reacting component may catalyze the sol-gel ceramic condensation.
  • organotitanates may catalyze urethane-forming reactions between isocyanates and polyols or an organic amine employed in a reaction with polyisocyanate or polyepoxide may catalyze the alkoxysilane condensation.
  • a particular example of such a system has a 3 -GP S derived ceramic network and an amine terminated polyether such as Jeffamine(R) M600 or M2005 (poly(oxypropylene) diamines), such as described in L.
  • polymer chain segments may be covalently bound to the polymer chains that provide a covalent linkage to a ceramic phase (e.g., in a block copolymer) or another polymer may be provided as a blending component of the composition to modify the physical or chemical properties of the composition.
  • Such polymer chain segments may be selected from the polymers listed above.
  • the additional polymer chain segments may be provided, for various reasons. For instance, the polymer chain segments may be introduced (a) to render the composite regions more hydrophilic or hydrophobic, (b) to modulate the release profile of therapeutic agent, if any, (c) to affect the mechanical characteristic of the material, and so forth.
  • Pebax® 4033 pellets are dissolved in 1-butanol/1-propanol (70/30 ratio) at reflux temperature for 4 hours.
  • Casting solutions are dropped into Petri dishes.
  • the solvent is evaporated in an oven at 70[deg.]C. Further drying takes place in a vacuum oven at 80°C for 1 day.
  • microscopy of the resulting films shows elongated separated domains of the inorganic sol-gel derived ceramic component that increased in domain size from the 15/85 TEOS/polymer film, Fig 2a , to the 25/75 TEOS/polymer film.
  • the films are useful as tough abrasion resistant coatings for catheters and balloons, for instance catheters and balloons of nylon or polyether block amide polymers.
  • the medical devices of the present invention optionally contain one or more therapeutic agents.
  • therapeutic agents include genetic therapeutic agents, non-genetic therapeutic agents and cells.
  • therapeutic agents include paclitaxel, sirolimus, everolimus, tacrolimus, Epo D, dexamethasone, estradiol, halofuginone, cilostazole, geldanamycin, ABT-578 (Abbott Laboratories), trapidil, liprostin, Actinomcin D, Resten-NG, Ap-17, abciximab, clopidogrel, Ridogrel, beta-blockers, bARKct inhibitors, phospholamban inhibitors, and Serca 2 gene/protein among others.
  • Numerous additional therapeutic agents useful for the practice of the present invention are also disclosed in U.S. Patent Application 2004/0175406 .
  • a wide range of therapeutic agent loadings can be used in connection with the medical devices of the present invention, with the therapeutically effective amount being readily determined by those of ordinary skill in the art and ultimately depending, for example, upon the condition to be treated, the age, sex and condition of the patient, the nature of the therapeutic agent, the nature of the composite region(s), the nature of the medical device, and so forth.
  • various techniques described above involve hydrolysis and condensation, which leads to the formation of a suspension containing a ceramic phase, which is analogous to the "sol” that is formed in sol-gel processing.
  • This suspension also includes a polymer in several techniques. Subsequent removal of water (as well as any other solvent species that may be present), results in the formation of a solid phase, which is analogous to the "gel” in sol-gel processing.
  • such a suspension may be used to directly form a medical device or a medical device component, followed by water/solvent removal.
  • the suspension may be dried and heated to form a melt for further processing.
  • Useful techniques for processing suspensions include pouring, spraying, spray coating, coating with an applicator (e.g., by roller or brush), spin-coating, dip-coating, web coating, techniques involving coating via mechanical suspension including air suspension, ink jet techniques, electrostatic techniques, and combinations of these processes.
  • Useful thermoplastic techniques for processing melts include compression molding, injection molding, blow molding, spinning, vacuum forming and calendaring, as well as extrusion into sheets, fibers, rods, tubes and other cross-sectional profiles of various lengths, and combinations of these processes.
  • the suspension or melt is applied to a substrate to form a composite region.
  • the substrate can correspond, for example, to all or a portion of an implantable or insertable medical device (e.g., a balloon, guide wire or stent, among many others) to which the suspension or melt is applied.
  • the substrate can also correspond, for example, to a template, such as a mold, from which the composite region is removed after solidification.
  • a template such as a mold
  • composite regions for medical devices are formed without the aid of a substrate.
  • therapeutic agents and/or any other optional agents
  • therapeutic and/or other optional agents can be introduced subsequent to the formation of the composite region in some embodiments.
  • the therapeutic agent is dissolved or dispersed within a solvent, and the resulting solution contacted with a previously formed composite region (e.g., using one or more of the application techniques described above, such as dipping, spraying, etc.).
  • composite barrier regions are provided over therapeutic-agent-containing regions in some embodiments of the invention.
  • a composite region can be formed over a therapeutic-agent-containing region, for example, using one of the suspension- or melt-based techniques described above.
  • a previously formed composite region can be adhered over a therapeutic agent containing region.
  • the selection and ratio of the polymer and sol-gel derived ceramic components can be varied to produce a desired release rate of the therapeutic agent. Therefore in some aspects the invention is particularly directed to an implanted device, especially a stent, graft, valve, vascular access port, embolization device, myocardial plug, pacemaker lead, sutures, orthopedic prostheses, or the like, that is designed for long term residence in the body (for instance 6 months or more).

Claims (11)

  1. Dispositif médical comprenant une région composite, la région composite comprenant un polymère organique et un matériau céramique dérivé de solgel dans des phases séparées ou des phases bi-continues ou dans les deux, le dispositif médical étant un dispositif médical implantable ou insérable et le polymère organique comprenant des segments de polyamide.
  2. Dispositif médical selon la revendication 1, dans lequel le matériau céramique dérivé de sol-gel comprend un réseau d'oxyde de silicium, aluminium, zirconium, titane, étain, hafnium, tantale, molybdène, tungstène, rhénium ou iridium ou un mélange de cela.
  3. Dispositif médical selon la revendication 1 ou 2, dans lequel le polymère organique comprend en outre des segments de polyéther.
  4. Dispositif médical selon l'une quelconque des revendications 1 à 3, dans lequel la région composite comprend des liaisons covalentes entre le polymère et le matériau céramique dérivé de sol-gel.
  5. Dispositif médical selon l'une quelconque des revendications 1 à 4, dans lequel le matériau céramique comprend un oxyde métallique sélectionné d'oxyde de titane et oxyde de zirconium.
  6. Dispositif médical selon l'une quelconque des revendications 1 à 5, comprenant e outre un agent thérapeutique qui est disposé au-dedans ou au-dessous de la région composite.
  7. Dispositif médical selon la revendication 6, dans lequel l'agent thérapeutique est un agent anti-proliferatif.
  8. Dispositif médical selon l'une quelconque des revendications 1 à 7, dans lequel le dispositif médical est un cathéter ou ballonnet fait de nylon ou polyéther bloc amide et la région composite est un revêtement sur le dispositif.
  9. Dispositif médical selon l'une quelconque des revendications 1 à 7, dans lequel le dispositif médical est un cathéter, ballonnet ou stent, et la région composite est un revêtement sur le dispositif qui fournit de la résistance à l'abrasion.
  10. Dispositif médical selon l'une quelconque des revendications 1 à 7, dans lequel le dispositif médical est un ballonnet.
  11. Dispositif médical selon l'une quelconque des revendications 1 à 7, dans lequel le dispositif médical est sélectionné d'un ballonnet, un fil guide, un filtre veine cave, un stent, un stent greffon, un greffon vasculaire, une bobine remplissant un anévrisme cérébral, un bouchon de myocarde, une valve de coeur, une valve vasculaire et un cadre de construction de tissu.
EP20060717874 2005-03-30 2006-01-10 Materiaux composites a base de polymere et de ceramique destines a etre utilises dans des dispositifs medicaux Not-in-force EP1871438B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/094,638 US9125968B2 (en) 2005-03-30 2005-03-30 Polymeric/ceramic composite materials for use in medical devices
PCT/US2006/000727 WO2006107359A1 (fr) 2005-03-30 2006-01-10 Materiaux composites a base de polymere et de ceramique destines a etre utilises dans des dispositifs medicaux

Publications (2)

Publication Number Publication Date
EP1871438A1 EP1871438A1 (fr) 2008-01-02
EP1871438B1 true EP1871438B1 (fr) 2011-05-18

Family

ID=36636312

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20060717874 Not-in-force EP1871438B1 (fr) 2005-03-30 2006-01-10 Materiaux composites a base de polymere et de ceramique destines a etre utilises dans des dispositifs medicaux

Country Status (6)

Country Link
US (1) US9125968B2 (fr)
EP (1) EP1871438B1 (fr)
JP (1) JP2008534121A (fr)
AT (1) ATE509643T1 (fr)
CA (1) CA2602451A1 (fr)
WO (1) WO2006107359A1 (fr)

Families Citing this family (85)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7713297B2 (en) 1998-04-11 2010-05-11 Boston Scientific Scimed, Inc. Drug-releasing stent with ceramic-containing layer
AU2002345328A1 (en) 2001-06-27 2003-03-03 Remon Medical Technologies Ltd. Method and device for electrochemical formation of therapeutic species in vivo
CN101090744B (zh) * 2005-01-21 2011-06-15 泰尔茂株式会社 导管及其制造方法
US9125968B2 (en) 2005-03-30 2015-09-08 Boston Scientific Scimed, Inc. Polymeric/ceramic composite materials for use in medical devices
US7914809B2 (en) * 2005-08-26 2011-03-29 Boston Scientific Scimed, Inc. Lubricious composites for medical devices
US8008395B2 (en) * 2005-09-27 2011-08-30 Boston Scientific Scimed, Inc. Organic-inorganic hybrid particle material and polymer compositions containing same
US8840660B2 (en) 2006-01-05 2014-09-23 Boston Scientific Scimed, Inc. Bioerodible endoprostheses and methods of making the same
US8440214B2 (en) 2006-01-31 2013-05-14 Boston Scientific Scimed, Inc. Medical devices for therapeutic agent delivery with polymeric regions that contain copolymers having both soft segments and uniform length hard segments
US8089029B2 (en) 2006-02-01 2012-01-03 Boston Scientific Scimed, Inc. Bioabsorbable metal medical device and method of manufacture
US20070224235A1 (en) 2006-03-24 2007-09-27 Barron Tenney Medical devices having nanoporous coatings for controlled therapeutic agent delivery
US8187620B2 (en) 2006-03-27 2012-05-29 Boston Scientific Scimed, Inc. Medical devices comprising a porous metal oxide or metal material and a polymer coating for delivering therapeutic agents
US8048150B2 (en) 2006-04-12 2011-11-01 Boston Scientific Scimed, Inc. Endoprosthesis having a fiber meshwork disposed thereon
US8815275B2 (en) 2006-06-28 2014-08-26 Boston Scientific Scimed, Inc. Coatings for medical devices comprising a therapeutic agent and a metallic material
EP2032091A2 (fr) 2006-06-29 2009-03-11 Boston Scientific Limited Dispositifs médicaux avec revêtement sélectif
JP2009545407A (ja) 2006-08-02 2009-12-24 ボストン サイエンティフィック サイムド，インコーポレイテッド 三次元分解制御を備えたエンドプロテーゼ
US20080050415A1 (en) * 2006-08-25 2008-02-28 Boston Scientic Scimed, Inc. Polymeric/ceramic composite materials for use in medical devices
CA2662162A1 (fr) * 2006-08-30 2008-03-06 The University Of British Columbia Revetements composites bioceramiques et procedes de fabrication
US8507639B2 (en) * 2006-09-11 2013-08-13 Boston Scientific Scimed, Inc. Radiopaque amide polymers and medical devices formed thereof
ATE508708T1 (de) 2006-09-14 2011-05-15 Boston Scient Ltd Medizinprodukte mit wirkstofffreisetzender beschichtung
JP2010503485A (ja) 2006-09-15 2010-02-04 ボストン サイエンティフィック リミテッド 医療用デバイスおよび同デバイスの製造方法
ATE517590T1 (de) 2006-09-15 2011-08-15 Boston Scient Ltd Biologisch erodierbare endoprothesen
ES2368125T3 (es) 2006-09-15 2011-11-14 Boston Scientific Scimed, Inc. Endoprótesis bioerosionable con capas inorgánicas bioestables.
US8808726B2 (en) 2006-09-15 2014-08-19 Boston Scientific Scimed. Inc. Bioerodible endoprostheses and methods of making the same
US8002821B2 (en) 2006-09-18 2011-08-23 Boston Scientific Scimed, Inc. Bioerodible metallic ENDOPROSTHESES
US7981150B2 (en) 2006-11-09 2011-07-19 Boston Scientific Scimed, Inc. Endoprosthesis with coatings
US9700704B2 (en) 2006-11-20 2017-07-11 Lutonix, Inc. Drug releasing coatings for balloon catheters
US8414910B2 (en) 2006-11-20 2013-04-09 Lutonix, Inc. Drug releasing coatings for medical devices
US8425459B2 (en) 2006-11-20 2013-04-23 Lutonix, Inc. Medical device rapid drug releasing coatings comprising a therapeutic agent and a contrast agent
US8414525B2 (en) 2006-11-20 2013-04-09 Lutonix, Inc. Drug releasing coatings for medical devices
US20080175887A1 (en) 2006-11-20 2008-07-24 Lixiao Wang Treatment of Asthma and Chronic Obstructive Pulmonary Disease With Anti-proliferate and Anti-inflammatory Drugs
US8998846B2 (en) 2006-11-20 2015-04-07 Lutonix, Inc. Drug releasing coatings for balloon catheters
US9737640B2 (en) 2006-11-20 2017-08-22 Lutonix, Inc. Drug releasing coatings for medical devices
US20080276935A1 (en) 2006-11-20 2008-11-13 Lixiao Wang Treatment of asthma and chronic obstructive pulmonary disease with anti-proliferate and anti-inflammatory drugs
US8414526B2 (en) 2006-11-20 2013-04-09 Lutonix, Inc. Medical device rapid drug releasing coatings comprising oils, fatty acids, and/or lipids
ATE488259T1 (de) 2006-12-28 2010-12-15 Boston Scient Ltd Bioerodierbare endoprothesen und herstellungsverfahren dafür
US8431149B2 (en) 2007-03-01 2013-04-30 Boston Scientific Scimed, Inc. Coated medical devices for abluminal drug delivery
US8070797B2 (en) 2007-03-01 2011-12-06 Boston Scientific Scimed, Inc. Medical device with a porous surface for delivery of a therapeutic agent
US8343740B2 (en) * 2007-03-29 2013-01-01 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Micro-organ device
US8067054B2 (en) * 2007-04-05 2011-11-29 Boston Scientific Scimed, Inc. Stents with ceramic drug reservoir layer and methods of making and using the same
US20080287984A1 (en) * 2007-05-18 2008-11-20 Jan Weber Medical balloons and methods of making the same
US7976915B2 (en) 2007-05-23 2011-07-12 Boston Scientific Scimed, Inc. Endoprosthesis with select ceramic morphology
US8002823B2 (en) 2007-07-11 2011-08-23 Boston Scientific Scimed, Inc. Endoprosthesis coating
US7942926B2 (en) 2007-07-11 2011-05-17 Boston Scientific Scimed, Inc. Endoprosthesis coating
EP2187988B1 (fr) 2007-07-19 2013-08-21 Boston Scientific Limited Endoprothese pourvue d'une surface anti-encrassement
US8852620B2 (en) * 2007-07-20 2014-10-07 Medtronic Vascular, Inc. Medical devices comprising polymeric drug delivery systems with drug solubility gradients
US20090028785A1 (en) * 2007-07-23 2009-01-29 Boston Scientific Scimed, Inc. Medical devices with coatings for delivery of a therapeutic agent
US8815273B2 (en) 2007-07-27 2014-08-26 Boston Scientific Scimed, Inc. Drug eluting medical devices having porous layers
US7931683B2 (en) 2007-07-27 2011-04-26 Boston Scientific Scimed, Inc. Articles having ceramic coated surfaces
WO2009018340A2 (fr) 2007-07-31 2009-02-05 Boston Scientific Scimed, Inc. Revêtement de dispositif médical par placage au laser
WO2009020520A1 (fr) 2007-08-03 2009-02-12 Boston Scientific Scimed, Inc. Revêtement pour un dispositif médical ayant une aire surfacique accrue
GB0717516D0 (en) * 2007-09-07 2007-10-17 Imp Innovations Ltd Bioactive nanocomposite material
US8052745B2 (en) 2007-09-13 2011-11-08 Boston Scientific Scimed, Inc. Endoprosthesis
US20090104474A1 (en) * 2007-10-17 2009-04-23 Princeton University Functionalized substrates and methods of making same
EP2222893B1 (fr) * 2007-10-19 2017-01-04 Biointraface, Inc. Procédé de revêtement
US8029554B2 (en) 2007-11-02 2011-10-04 Boston Scientific Scimed, Inc. Stent with embedded material
US7938855B2 (en) 2007-11-02 2011-05-10 Boston Scientific Scimed, Inc. Deformable underlayer for stent
US8216632B2 (en) 2007-11-02 2012-07-10 Boston Scientific Scimed, Inc. Endoprosthesis coating
US9114125B2 (en) * 2008-04-11 2015-08-25 Celonova Biosciences, Inc. Drug eluting expandable devices
US8920491B2 (en) 2008-04-22 2014-12-30 Boston Scientific Scimed, Inc. Medical devices having a coating of inorganic material
US8932346B2 (en) 2008-04-24 2015-01-13 Boston Scientific Scimed, Inc. Medical devices having inorganic particle layers
US7998192B2 (en) 2008-05-09 2011-08-16 Boston Scientific Scimed, Inc. Endoprostheses
US20090306769A1 (en) * 2008-06-06 2009-12-10 Boston Scientific Scimed, Inc. Medical balloon made with hybrid polymer-ceramic material and method of making and using the same
US8236046B2 (en) 2008-06-10 2012-08-07 Boston Scientific Scimed, Inc. Bioerodible endoprosthesis
EP2303350A2 (fr) 2008-06-18 2011-04-06 Boston Scientific Scimed, Inc. Revêtement d'endoprothèse
US7985252B2 (en) 2008-07-30 2011-07-26 Boston Scientific Scimed, Inc. Bioerodible endoprosthesis
WO2010024898A2 (fr) 2008-08-29 2010-03-04 Lutonix, Inc. Procédés et appareils pour poser un revêtement sur des cathéters à ballonnet
US8076529B2 (en) 2008-09-26 2011-12-13 Abbott Cardiovascular Systems, Inc. Expandable member formed of a fibrous matrix for intraluminal drug delivery
US8226603B2 (en) 2008-09-25 2012-07-24 Abbott Cardiovascular Systems Inc. Expandable member having a covering formed of a fibrous matrix for intraluminal drug delivery
US8049061B2 (en) 2008-09-25 2011-11-01 Abbott Cardiovascular Systems, Inc. Expandable member formed of a fibrous matrix having hydrogel polymer for intraluminal drug delivery
US8500687B2 (en) 2008-09-25 2013-08-06 Abbott Cardiovascular Systems Inc. Stent delivery system having a fibrous matrix covering with improved stent retention
US8382824B2 (en) 2008-10-03 2013-02-26 Boston Scientific Scimed, Inc. Medical implant having NANO-crystal grains with barrier layers of metal nitrides or fluorides
US8389083B2 (en) * 2008-10-17 2013-03-05 Boston Scientific Scimed, Inc. Polymer coatings with catalyst for medical devices
US20100100115A1 (en) * 2008-10-20 2010-04-22 Wilson-Cook Medical Inc. Foam filled intragastric balloon for treating obesity
US8231980B2 (en) 2008-12-03 2012-07-31 Boston Scientific Scimed, Inc. Medical implants including iridium oxide
TWI377226B (en) * 2008-12-31 2012-11-21 Far Eastern New Century Corp Poly (lactic acid) resin composition for preparing transparent and impact-resistant article, article prepared therefrom and preparation process thereof
EP2403546A2 (fr) 2009-03-02 2012-01-11 Boston Scientific Scimed, Inc. Implants médicaux à tamponnage spontané
US8071156B2 (en) 2009-03-04 2011-12-06 Boston Scientific Scimed, Inc. Endoprostheses
US8287937B2 (en) 2009-04-24 2012-10-16 Boston Scientific Scimed, Inc. Endoprosthese
US8668732B2 (en) 2010-03-23 2014-03-11 Boston Scientific Scimed, Inc. Surface treated bioerodible metal endoprostheses
JP6655785B2 (ja) * 2014-04-17 2020-02-26 パナソニックＩｐマネジメント株式会社 樹脂組成物およびその製造方法並びに半導体装置
JP6442860B2 (ja) * 2014-04-23 2018-12-26 株式会社リコー 前駆体ゾルゲル溶液、電気機械変換素子、液滴吐出ヘッド、及びインクジェット記録装置
US10246594B2 (en) 2016-07-20 2019-04-02 The Boeing Company Corrosion inhibitor-incorporated layered double hydroxide and sol-gel coating compositions and related processes
US10246593B2 (en) 2016-07-20 2019-04-02 The Boeing Company Sol-gel coating compositions including corrosion inhibitor-encapsulated layered double hydroxide and related processes
US10428226B2 (en) 2016-07-20 2019-10-01 The Boeing Company Sol-gel coating compositions and related processes
US10421869B2 (en) 2017-01-09 2019-09-24 The Boeing Company Sol-gel coating compositions including corrosion inhibitor-encapsulated layered metal phosphates and related processes

Family Cites Families (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2490691A (en) 1946-10-03 1949-12-06 Du Pont Alkyl polysilicates
BE794718Q (fr) 1968-12-20 1973-05-16 Dow Corning Ltd Procede de reticulation d'olefines
US3950285A (en) 1974-04-04 1976-04-13 Atlantic Richfield Company Preparation of polymeric urethanes from dicarbamates
GB8400149D0 (en) 1984-01-05 1984-02-08 Bp Chem Int Ltd Polymer composition
JPS60231757A (ja) 1984-05-01 1985-11-18 Toray Ind Inc ポリエステル組成物
GB8514330D0 (en) 1985-06-06 1985-07-10 Bp Chem Int Ltd Polymer composition
US5109080A (en) 1989-10-06 1992-04-28 Virginia Tech Intellectual Properties, Inc. High refractive-index ceramic/polymer hybrid material
US4950779A (en) 1989-12-04 1990-08-21 General Electric Company Nonaqueous method for making silicone oligomers
US5178158A (en) * 1990-10-29 1993-01-12 Boston Scientific Corporation Convertible guidewire-catheter with soft tip
EP0518057B1 (fr) 1991-06-08 1998-07-29 Hüls Aktiengesellschaft Mélanges d'oligomères linéaires et cycliques de siloxanes, leur préparation et leur utilisation
US5252654A (en) 1991-07-03 1993-10-12 E. I. Du Pont De Nemours And Company Organic-inorganic polymeric composites
US5336731A (en) 1991-10-30 1994-08-09 Quantum Chemical Corporation Fractional melt flow rate polymer powders and process for their preparation
US5210168A (en) 1992-04-02 1993-05-11 Dow Corning Corporation Process for forming siloxane bonds
US5354802A (en) 1993-02-11 1994-10-11 Polyplastics Co., Ltd. Resin composition for blow molding and blow molded item made therefrom
WO1994023787A1 (fr) * 1993-04-22 1994-10-27 Rammler David H Catheter a ballon de prelevement
EP0661558A1 (fr) 1993-12-29 1995-07-05 Minnesota Mining And Manufacturing Company Sol gel polymère-céramique
US5824622A (en) 1994-01-12 1998-10-20 E. I. Du Pont De Nemours And Company Porous microcomposite of perfluorinated ion-exchange polymer and metal oxide, a network of silica, or a network of metal oxide and silica derived via a sol-gel process
US6146356A (en) 1994-03-02 2000-11-14 Scimed Life Systems, Inc. Block copolymer elastomer catheter balloons
US5830182A (en) 1994-03-02 1998-11-03 Scimed Life Systems, Inc. Block copolymer elastomer catheter balloons
US5951941A (en) 1994-03-02 1999-09-14 Scimed Life Systems, Inc. Block copolymer elastomer catheter balloons
DK0748232T4 (da) 1994-03-02 2009-01-19 Boston Scient Scimed Inc Kateterballoner af blokcopolymerelastomerer
US5985356A (en) 1994-10-18 1999-11-16 The Regents Of The University Of California Combinatorial synthesis of novel materials
DE4437424A1 (de) 1994-10-20 1996-04-25 Hoechst Ag Aerogelhaltige Zusammensetzung, Verfahren zu ihrer Herstellung sowie ihre Verwendung
CA2161712A1 (fr) 1994-11-03 1996-05-04 Ketan N. Shah Compositions elastomeres modifiees au silane et articles obtenus a l'aide de ces compositions
US5840387A (en) 1995-07-28 1998-11-24 Aegis Biosciences L.L.C. Sulfonated multiblock copolymer and uses therefor
JP3380994B2 (ja) 1995-12-13 2003-02-24 西川ゴム工業株式会社 ポリヒドロキシカルボン酸樹脂の製造方法
SE9602529D0 (sv) * 1996-06-26 1996-06-26 Astra Ab Medical device
US6013855A (en) 1996-08-06 2000-01-11 United States Surgical Grafting of biocompatible hydrophilic polymers onto inorganic and metal surfaces
US5849215A (en) 1997-01-08 1998-12-15 The Regents Of The University Of California Highly ordered nanocomposites via a monomer self-assembly in situ condensation approach
JP4291415B2 (ja) 1997-02-25 2009-07-08 バイエル・アクチエンゲゼルシヤフト 有機−無機ハイブリッド材料
US6232386B1 (en) 1997-02-26 2001-05-15 Integument Technologies, Inc. Polymer composites having an oxyhalo surface and methods for making same
AU734159B2 (en) 1997-02-26 2001-06-07 Integument Technologies, Inc. Polymer composites and methods for making and using same
US6548590B1 (en) 2000-03-22 2003-04-15 Integument Technologies, Inc. Polymer and inorganic-organic hybrid composites and methods for making and using same
US5977241A (en) 1997-02-26 1999-11-02 Integument Technologies, Inc. Polymer and inorganic-organic hybrid composites and methods for making same
US5977204A (en) 1997-04-11 1999-11-02 Osteobiologics, Inc. Biodegradable implant material comprising bioactive ceramic
DE19821665A1 (de) 1997-05-28 1998-12-03 Basf Ag Compositpigmente auf Basis von polyalkylenpolyaminmodifizierten nanopartikulären Metalloxiden und anionischen Farbstoffen
US6599664B2 (en) 1997-08-22 2003-07-29 Yardney Technical Products, Inc. Inorganic gel-polymer electrolyte
US6093463A (en) 1997-12-12 2000-07-25 Intella Interventional Systems, Inc. Medical devices made from improved polymer blends
US6140445A (en) 1998-04-17 2000-10-31 Crompton Corporation Silane functional oligomer
JP2002517585A (ja) 1998-06-05 2002-06-18 カボット・コーポレーション ナノ多孔質相互浸透有機−無機網目構造
JP3897938B2 (ja) 1998-10-22 2007-03-28 宇部日東化成株式会社 有機−無機複合傾斜材料、その製造方法及びその用途
US6686035B2 (en) 1999-02-05 2004-02-03 Waters Investments Limited Porous inorganic/organic hybrid particles for chromatographic separations and process for their preparation
AU2699800A (en) 1999-02-16 2000-09-04 Isotis B.V. Organoceramics
FR2791062B1 (fr) 1999-03-15 2003-09-12 Multibase Sa Reticulation de polymeres ou copolymeres de l'acetate de vinyle, elaboration d'elastomeres thermoplastiques reticules dynamiquement et de materiaux hybrides organiques-inorganiques
US6395226B1 (en) 1999-04-06 2002-05-28 Medtronic, Inc. Alkoxysilane/alkysilane copolymer coating of medical devices
JP4214203B2 (ja) 1999-05-18 2009-01-28 オリヱント化学工業株式会社 有機−無機複合材料およびその製造方法
MXPA02004017A (es) 1999-10-21 2003-09-25 Dow Global Technologies Inc Composiciones inorganicas/organicas.
US6472467B1 (en) 1999-10-21 2002-10-29 Dow Global Technologies Inc. Inorganic/organic compositions
US6946174B1 (en) 2000-10-12 2005-09-20 Boston Scientific Scimed, Inc. Moisture curable balloon materials
US6444324B1 (en) 2000-12-01 2002-09-03 Scimed Life Systems, Inc. Lubricated catheter balloon
US6545097B2 (en) 2000-12-12 2003-04-08 Scimed Life Systems, Inc. Drug delivery compositions and medical devices containing block copolymer
US6569958B1 (en) 2001-10-19 2003-05-27 Dow Corning Corporation Thermoplastic silicone elastomers from compatibilized polyester resins
US8337893B2 (en) 2002-07-10 2012-12-25 Florida Research Foundation, Inc, University Of Sol-gel derived bioactive glass polymer composite
DK1521603T3 (da) * 2002-07-12 2011-04-18 Cook Inc Coated medicinsk anordning
JP3765789B2 (ja) 2002-12-12 2006-04-12 電気化学工業株式会社 シリカ複合化ラテックス組成物、シリカ複合化ポリクロロプレン系組成物及び製造方法
US8313759B2 (en) 2003-03-06 2012-11-20 Boston Scientific Scimed, Inc. Implantable or insertable medical devices containing miscible polymer blends for controlled delivery of a therapeutic agent
US7250041B2 (en) * 2003-03-12 2007-07-31 Abbott Cardiovascular Systems Inc. Retrograde pressure regulated infusion
US7335185B2 (en) 2003-07-18 2008-02-26 Boston Scientific Scimed, Inc. Protective coatings for medical devices
US7981441B2 (en) * 2004-02-18 2011-07-19 The Board Of Trustees Of The Leland Stanford Junior University Drug delivery systems using mesoporous oxide films
DE102004012411A1 (de) 2004-03-13 2005-09-29 Dot Gmbh Kompositmaterialien auf der Basis von Polykieselsäuren und Verfahren zu deren Herstellung
US20060199876A1 (en) * 2005-03-04 2006-09-07 The University Of British Columbia Bioceramic composite coatings and process for making same
US9125968B2 (en) 2005-03-30 2015-09-08 Boston Scientific Scimed, Inc. Polymeric/ceramic composite materials for use in medical devices
US7914809B2 (en) 2005-08-26 2011-03-29 Boston Scientific Scimed, Inc. Lubricious composites for medical devices
US7365126B2 (en) 2005-09-16 2008-04-29 Boston Scientific Scimed, Inc. Medical device articles formed from polymer-inorganic hybrids prepared by ester-alkoxy transesterification reaction during melt processing
US8008395B2 (en) 2005-09-27 2011-08-30 Boston Scientific Scimed, Inc. Organic-inorganic hybrid particle material and polymer compositions containing same
US20090306769A1 (en) 2008-06-06 2009-12-10 Boston Scientific Scimed, Inc. Medical balloon made with hybrid polymer-ceramic material and method of making and using the same

Also Published As

Publication number Publication date
US20060230476A1 (en) 2006-10-12
ATE509643T1 (de) 2011-06-15
US9125968B2 (en) 2015-09-08
EP1871438A1 (fr) 2008-01-02
CA2602451A1 (fr) 2006-10-12
WO2006107359A1 (fr) 2006-10-12
JP2008534121A (ja) 2008-08-28

Similar Documents

Publication Publication Date Title
EP1871438B1 (fr) Materiaux composites a base de polymere et de ceramique destines a etre utilises dans des dispositifs medicaux
EP2408487B1 (fr) Matériaux composites polymères/inorganiques pour utilisation dans des dispositifs médicaux
US7914809B2 (en) Lubricious composites for medical devices
EP1940921B1 (fr) Materiau particulaire hybride organique-inorganique et compositions polymeres contenant celui-ci
US20090306769A1 (en) Medical balloon made with hybrid polymer-ceramic material and method of making and using the same
US7931683B2 (en) Articles having ceramic coated surfaces
US7553546B1 (en) Polyethylene oxide and silicone copolymers and their usage on medical devices
US7715922B1 (en) Polyethylene oxide and polyisobutylene copolymers and their usage on medical devices
US8075906B2 (en) Medical devices having polymeric regions with copolymers containing hydrocarbon and heteroatom-containing monomeric species
US20070207182A1 (en) Medical devices having electrically aligned elongated particles
US20080175881A1 (en) Blood-contacting medical devices for the release of nitric oxide and anti-restenotic agents
EP2842582A2 (fr) Dispositifs médicaux contenant des particules de silicate et de carbone
JP2009525125A (ja) ソフトセグメントと均一長さのハードセグメントの両者を有する共重合体含有ポリマー領域を持つ治療薬送達用医療器具
US7708774B1 (en) Polyethylene oxide and silicone copolymers and their usage on medical devices

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20071019

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20090407

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602006022046

Country of ref document: DE

Effective date: 20110630

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20110518

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110919

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110918

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110829

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110819

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20120221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602006022046

Country of ref document: DE

Effective date: 20120221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20120110

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20120928

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120110

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110518

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120110

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060110

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602006022046

Country of ref document: DE

Representative=s name: VOSSIUS & PARTNER PATENTANWAELTE RECHTSANWAELT, DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602006022046

Country of ref document: DE

Representative=s name: VOSSIUS & PARTNER PATENTANWAELTE RECHTSANWAELT, DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602006022046

Country of ref document: DE

Owner name: BOSTON SCIENTIFIC LIMITED, BM

Free format text: FORMER OWNER: BOSTON SCIENTIFIC LTD., HASTINGS, CHRIST CHURCH, BB

Effective date: 20150202

Ref country code: DE

Ref legal event code: R082

Ref document number: 602006022046

Country of ref document: DE

Representative=s name: VOSSIUS & PARTNER PATENTANWAELTE RECHTSANWAELT, DE

Effective date: 20150202

Ref country code: DE

Ref legal event code: R082

Ref document number: 602006022046

Country of ref document: DE

Representative=s name: VOSSIUS & PARTNER PATENTANWAELTE RECHTSANWAELT, DE

Effective date: 20141026

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20170104

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IE

Payment date: 20170109

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602006022046

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180801

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180110